Single catalyst systems having a scorpion-like structure

ABSTRACT

The present invention discloses single site catalyst systems having scorpion-like three dimensional structure that are suitable for oligomerising or polymerising ethylene and alpha-olefins.

The present invention related to the field of single site catalyst systems having scorpion-like three dimensional structure that are suitable for oligomerising or polymerising ethylene and alpha-olefins.

There exists a multitude of catalyst systems available for polymerising or oligomerising ethylene and alpha-olefins, but there is a growing need for finding new systems capable to tailor polymers with very specific properties. More and more post-metallocene catalyst components based on early or late transition metals from Groups 3 to 10 of the Periodic Table have recently been investigated such as for example those disclosed in Gibson and al. review (Gibson, V. C.; Spitzmesser, S. K., Chem. Rev. 2003, 103, p. 283). But there is still a need to improve either the specificities or the performances of these systems.

It is an aim of the present invention to provide a new single site catalyst components based on beta-diimine ligands with a chelating pendant arm.

It is also an aim of the present invention to provide single site catalyst components having a scorpion-like spatial organisation.

It is another aim of the present invention to provide active catalyst systems based on these catalyst components.

It is a further aim of the present invention to provide a process for polymerising or for oligomerising ethylene and alpha-olefins with these new catalyst systems.

It is also an aim of the present invention to provide a polyethylene by polymerising ethylene with these new catalyst systems.

Accordingly, the present invention discloses a ligand of formula I

wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are each independently selected from hydrogen, unsubstituted or substituted hydrocarbyl, or inert functional group. Two or more of those the groups can themselves be linked together to form further ring or rings.

R1 and R3, R2 and R4, and R9 and R10, cannot be simultaneously oxazoline

wherein Z is selected from groups 15 or 16 of the Periodic Table and m is the valence of Z minus one.

By inert functional group, is meant a group, other than hydrocarbyl or substituted hydrocarbyl, that is inert under the complexation conditions to which the compound containing said group is subjected. They can be selected for example from halo, ester, ether, amino, imino, nitro, cyano, carboxyl, phosphate, phosphonite, phosphine, phosphinite, thioether and amide. Preferably, they are selected from halo, such as chloro, bromo, fluoro and iodo, or ether of formula—OR* wherein R* is unsubstituted or substituted hydrocarbyl. After metallation of the ligand, an inert functional group must not coordinate to the metal more strongly than the groups organised to coordinate to the metal and thereby displace the desired coordinating group.

It results from the reaction between a beta-diimine II and a compound of formula III wherein X is a leaving group, preferably halogen for example Br.

Preferably, R1 and R2 are the same or different and are unsubstituted or substituted alkyl groups, unsubstituted or substituted aryl groups, or unsubstituted or substituted cycloalkyl groups, more preferably, they are unsubstituted or substituted phenyl groups and if they are substituted, the substituents may be joined to form a closed structure. If the phenyls are substituted, the substituents preferably occupy 2 and 6 positions.

Preferably, R3 and R4 are the same or different, hydrogen, unsubstituted or substituted alkyl groups, unsubstituted or substituted aryl groups, or unsubstituted or substituted cycloalkyl groups, more preferably, they are unsubstituted or substituted alkyl groups. Optionally R3 and R4 may also be linked together to form a cyclohexyl ring.

In another embodiment according to the present invention, R1 with R3 or R2 with R4 are linked together to form a ring.

Preferably, R5 is hydrogen, unsubstituted or substituted alkyl groups, unsubstituted or substituted aryl groups, more preferably hydrogen or methyl.

Preferably, Z is selected from N, P, O or S.

Preferably, R6, R7, R8, R9 and R10 are the same or different, hydrogen, unsubstituted or substituted alkyl groups, unsubstituted or substituted aryl groups, or unsubstituted or substituted cycloalkyl groups. R8, R9 and R10 can be linked together to form a ring, for example a pyridine, a quinoline, an isoquinoline, a pyrrolyl, a furyl or a thiophenyl group.

Examples of formula III include 2-(bromomethyl)-5-nitrofuran, 2-(bromomethyl)-1,3-dioxalane, 2-(bromomethyl)tetrahydro-2H-pyran, 2-(bromomethyl)-5-trifluoromethyl)furan, 3(-bromomethyl)pyridazine, 2-bromomethylpyridine, 1-bromo-2-ethoxyethane, 2-bromoethylacetate, 1-bromo-2-(2-methoxyethoxy)ethane, [(2-bromoethoxy)methyl]benzene and 3-(bromomethyl)-2,4,10-trioxaadamantane, 2-bromo-N,N-dimethylaniline.

The invention also discloses a catalyst component of formula IV:

resulting from the complexation of ligand I with the metallic salt MX′_(n) in a solvent, wherein M is a metal Group 3 to 10 of the periodic Table, X′ is the same or different and can be a halogen, alcoholate, or substituted or unsubstituted hydrocarbyl and n is the valence of M.

Preferably, M is Ti, Zr, Hf, V, Cr, Mn, Fe, Co, Ni, Pd or rare earths. More preferably, it is Cr or Fe.

The metal is complexed with the two nitrogen atoms of the starting beta-diimine and during the complexation reaction, the complex folds around the carbon atom joining atom Z to the metal to form a three dimensional scorpion-like structure.

The solvent may be selected from dichloromethane or tetrahydrofuran and the complexation reaction is carried out at room temperature.

The present invention also discloses an active catalyst system comprising the single site catalyst component of formula IV and an activating agent having an ionising action.

Suitable activating agents are well known in the art. The activating agent can be an aluminium alkyl represented by formula AlR_(n) ⁺X_(3−n) wherein R⁺ is an alkyl having from 1 to 20 carbon atoms and X is a halogen. The preferred alkylating agents are triisobutyl aluminium (TIBAL) or triethyl aluminium (TEAL).

Alternatively, it can be aluminoxane and comprise oligomeric linear and/or cyclic alkyl aluminoxanes represented by formula

for oligomeric, linear aluminoxanes and by formula

for oligomeric, cyclic aluminoxane, wherein n is 1-40, preferably 1-20, m is 3-40, preferably 3-20 and R* is a C₁-C₈ alkyl group and preferably methyl or isobutyl.

Preferably, the activating agent is methylaluminoxane (MAO) or tetra-isobutyldialuminoxane (IBAO), more preferably, it is IBAO.

The amount of activating agent is selected to give an Al/M ratio of from 100 to 3000, preferably of from 500 to 2000. The amount of activating agent depends upon its nature, the preferred Al/M ratio being of about 2000.

Suitable boron-containing activating agents may comprise a triphenylcarbenium boronate such as tetrakis-pentafluorophenyl-borato-triphenylcarbenium as described in EP-A-0427696, or those of the general formula [L′-H]+[B Ar₁ Ar₂ X₃ X₄]— as described in EP-A-0277004 (page 6, line 30 to page 7, line 7).

The amount of boron-containing activating agent is selected to give a B/M ratio of from 0.5 to 5, preferably of about 1.

In another embodiment, according to the present invention, the single site catalyst component of formula IV may be deposited on a conventional support. Preferably, the conventional support is silica impregnated with MAO. It may also be an activating support such as a fluorided alumina silica.

The present invention further discloses a method for preparing an active catalyst system that comprises the steps of:

-   -   a) providing a beta-diimine ligand precursor of formula II;     -   b) reacting the beta-diimine ligand precursor of formula II with         compound III;     -   c) retrieving the scorpion-like ligand I     -   d) complexing the ligand obtained in step c) with a metallic         salt MX′_(n);     -   e) retrieving a catalyst component of formula IV;     -   f) activating with an activating agent having an ionising         action;     -   g) optionally adding a cocatalyst     -   h) retrieving an active oligomerisation or polymerisation         catalyst system.     -   Alternatively, in step f) catalyst component IV is deposited on         a support impregnated with an activating agent or on an         activating support containing fluor.

The cocatalyst may be selected from triethylaluminium, triisobutylaluminum, tris-n-octylaluminium, tetraisobutyldialuminoxane or diethyl zinc.

The active catalyst system is used in the oligomerisation and in the polymerisation of ethylene and alpha-olefins.

The present invention discloses a method for the oligomerisation or the homo- or co-polymerisation of ethylene and alpha-olefins that comprises the steps of:

-   -   a) injecting the active catalyst system into the reactor;     -   b) injecting the monomer and optional comonomer either before or         after or simultaneously with step a);     -   c) maintaining under polymerisation conditions;     -   d) retrieving the oligomers and/or polymer.

The pressure in the reactor can vary from 0.5 to 50 bars, preferably from 5 to 25 bars.

The polymerisation temperature can range from 10 to 100° C., preferably from 50 to 85° C.

The preferred monomer and optional comonomer can be selected from ethylene, propylene or 1-hexene. Alternatively, the optional comonomer can be a polar functionalised alpha-olefin.

With a catalyst activated by MAO, the polymer formed is characterized by a melting point comprised between 100 and 135° C., preferably between 125 and 131° C. as measured by Differential Scanning Calorimetry (DSC) method. It has a multimodal molecular weight distribution with a molecular weight Mw of from 50000 to 500000, preferably of from 75000 to 250000, and a molecular weight distribution of 15 to 50 depending on the solvent. The molecular weight distribution is measured by the polydispersity index D defined as the ratio Mw/Mn of the weight average molecular weight Mw over the number average molecular weight Mn. Molecular weights are measured by Gel Permeation Chromatography (GPC).

With a catalyst activated by IBAO, the polymer formed is characterised by a melting point of about 135° C. as measured by Differential Scanning Calorimetry (DSC) method. It has a broad monomodal molecular weight distribution with a molecular weight Mw of 765000, and a molecular weight distribution of 25. The molecular weight distribution is measured by the polydispersity index D defined as the ratio Mw/Mn of the weight average molecular weight Mw over the number average molecular weight Mn. Molecular weights are measured by Gel Permeation Chromatography (GPC). ¹³C NMR analysis showed the presence of linear (12 per 10000 carbon atoms) and isobutyle (10 per 10000 C atoms) saturated end chains. No short chain branching were detected.

With a supported catalyst, the polymer formed has a monomodal molecular weight distribution with a molecular weight Mw of from 150000 to 350000, preferably of from 180000 to 280000, and a molecular weight distribution of 5 to 20. It has a melting point comprised between 125 and 135° C. It has no short chain branching detectable by ¹³C NMR analysis but it has long chain branching. The presence of the long chain branching is indicated by RDA analysis.

Throughout this description, LCB means chains long enough for entanglements to occur.

In order to quantify LCB concentration with rheology, we have adapted Shroff and Mavridis definition of LCBI (Long Chain Branching Index) to our high molecular weight PE samples. (R. N. Shroff and H. Mavridis, Macromolecules, 32, 8454, 1999.) As explained by those authors, LCBI quantifies the rheological effect of LCB (enhancement of shear viscosity at low shear rates) for narrow and broad molecular weight distribution (MWD) samples with sparse amount of LCB, that is LCB concentration typically too low to be detected by ¹³C NMR (for homopolymers PE) or by solution techniques such as size exclusion chromatography (SEC) coupled with on-line viscosity or light scattering detectors. DRI (Dow Rheology Index) which is another LCB indicator described in lai et al. (S. Lai, T. A. Plumley, T. I. Butler, G. W. Knight, C. I. Kao, SPE Antec Techn. Papers, 40, 1814, 1994) is not suitable to quantify LCB in polyethylene resins with polydispersity index larger than 4. DRI is thus not suitable to gauge LCB in our PE resins with broad MWD.

According to those authors, LCBI is defined as the ratio of intrinsic viscosities of PE resins estimated by rheology to that determined via solution techniques.

${L\; C\; B\; I} = {\frac{\lbrack\eta\rbrack_{rheo}}{\lbrack\eta\rbrack_{sol}} - 1}$

wherein [η]_(rheo) and [η]_(sol) are the intrinsic viscosities obtained respectively from rheology or via solution.

Thus, LCBI is zero for linear samples and is above zero for polyethylene containing long chain branching. A high level of LCB is encountered with LCBI above 0.8. Instead of determining intrinsic viscosity from the relative viscosity at 0.2 dg/min as explained in their publication, we calculate intrinsic viscosity value via solution (expressed in dl/g) in terms of weight average molecular weight Mw (expressed in Da) obtained by size exclusion chromatography (SEC) with equation

[η]_(sol)=5.25*10⁻⁴(M _(w))^(0.76)

Zero shear viscosity (η₀) (expressed in Pa·s) is also related to M_(w) (expressed in Da) by equation

η₀=3.834*10⁻¹⁶(M _(w))^(3.855)

Zero shear viscosity is estimated by fitting with Carreau-Yasuda flow curve at 190° C., obtained by oscillatory shear rheology on ARES equipment in the linear viscoelasticity domain. Circular frequency (W in rad/s) varies from 0.05-0.1 rad/s to 250-500 rad/s and the shear strain is typically 10%.

The intrinsic viscosity inferred from rheology can thus be expressed as

$\eta = \frac{\eta_{0}}{\left( {1 + \left( {W*\tau} \right)^{b}} \right)^{({{({1 - n})}/b})}}$

wherein τ, b and n are fitting parameters called relaxation time, breadth parameter and power-law parameter, respectively.

The LCBI is thus rewritten as

${L\; C\; B\; I} = {\frac{0.5747*\left( \eta_{0} \right)^{0.19714}}{5.25*10^{- 4}\left( M_{w} \right)^{0.76}} - 1}$

In order to increase the accuracy in estimating zero shear viscosity, a frequency sweep experiment having a typical range of 0.1-250 rad/s, is combined with a creep experiment, in order to extend the frequency range to values down to 10⁻⁴ s⁻¹ or lower, and taking the usual assumption of equivalence of angular frequency (rad/s) and shear rate.

Frequency sweep experiments are performed using small parallel plates having a diameter of 8 mm that allow flow curve determination with as little as 0.1 g PE. Also, most tests are conducted at a temperature of 230° C. for polymers that do not exhibit homogeneous flow below that temperature.

Thus, LCBI is derived at a temperature of 230° C. using extrapolated shear viscosity at 0.001 s⁻¹ as follows.

${L\; C\; B\; I_{230}} = {\frac{0.58*\left( \eta_{0.001} \right)^{0.2096}}{5.25*10^{- 4}\left( M_{w} \right)^{0.76}} - 1}$

The subscript 230 recalls that LCBI is determined from frequency sweep experiments conducted at 230° C.

The relationship between viscosity and Mw is established as usual with a series of linear polyethylene. The viscosity/Mw relationship was established with a series of 15 linear PE having a polydispersity index between 2 and 18.

ZN or metallocene-produced polyethylene known to be linear have a LCBI of 0+/−0.1. Thus, PE with LCB are detected above LCBI of 0.1-0.2

LIST OF FIGURES

FIG. 1 represents the molecular weight distribution of the polyethylene obtained in example 5.

FIG. 2 represents the molecular weight distribution of the polyethylenes obtained in examples 9 and 11.

EXAMPLES Preparation of Catalyst Component Synthesis of the Ligand 1. Step 1.

The beta-diimine was synthesised according to the published procedure of Feldman and al. (Organometallics 1997, 16, p. 1514).

Step 2.

760 mg (3 mmol) of 2-bromomethylpyridine.HBr and 436 mg (3.15 mmol) of potassium carbonate were degassed under vacuum for 1 hour. 10 mL of dry acetone were added and the mixture was stirred under argon for 6 hours at room temperature (about 25° C.). The solvent was removed and the 2-bromomethylpyridine was extracted with 3×10 mL of diethyl ether under inert atmosphere. The solvent was removed to afford a pink oil with quantitative yield.

Step 3.

1.26 g (3 mmol) of beta-diimine were dissolved in 15 mL of dry THF under argon. The solution was cooled to a temperature of −20° C. and 2 mL (3.15 mmol) of n-BuLi (1.6 M in hexane) were added dropwise. The colourless solution turned immediately to bright yellow and was stirred at room temperature for 30 minutes. The solution was cooled to a temperature of −20° C. and a solution of 2-bromomethylpyridine in 10 mL of dry THF was added by canula. The solution was allowed to warm to room temperature and was stirred overnight, before being heated at 80° C. for 6 hours under reflux. After that time, the solvent was evaporated to dryness. The residue was taken with 10 mL of dichloromethane and filtered over neutral alumina. The solution was evaporated to afford a yellow oil purified by column chromatography (SiO₂, pentane:diethyl ether 95:5 to 80:20). 910 mg of the expected product were obtained as pale yellow oil containing isomers 1a and 1b, with a yield of 60%.

The isomers were characterised as follows:

C₃₅H₄₇N₃

M=509.77 g.mol⁻¹

¹H NMR (500 MHz, CDCl₃) results:

Isomer 1a: δ=1.10 (m, 12H, CH₃ iPr), 1.21 (dd, 12H, J=6.8 Hz, CH₃ iPr), 1.92 (s, 6H, CH₃CN), 2.53 (sept, 2H, J=6.8 Hz, CH iPr), 2.60 (sept, 2H, J=6.8 Hz, CH iPr), 3.65 (d, 2H, J=7.5 Hz, CH₂), 4.70 (t, 1H, J=7.5 Hz, CH), 7.11 (m, 2H, CH para Ph), 7.17 (br s, 4H, CH meta Ph), 7.22 (m, 1H, H5 pyr), 7.38 (d, 1H, J=7.5 Hz, H3 pyr), 7.66 (td, 1H, J=7.5 Hz, J=1.8 Hz, H4 pyr), 8.66 (d, 1H, J=5 Hz, H6 pyr).

Isomer 1b: δ=1.07 (m, 12H, CH₃ iPr), 1.13 (d, 12H, J=6.9 Hz, CH₃ iPr), 1.78 (s, 6H, CH₃CN), 3.20 (sept, 4H, J=6.9 Hz, CH iPr), 4.06 (s, 2H, CH₂), 7.09 (m, 2H, CH para Ph), 7.13 (m, 4H, CH meta Ph), 7.18 (m, 1H, H5 pyr), 7.33 (d, 1H, J=7.8 Hz, H3 pyr), 7.68 (m, 1H, H4 pyr), 8.61 (d, 1H, J=5 Hz, H6 pyr).

Preparation of Fe(II) Complex 2.

210 mg (0.4 mmol) of beta-diimine-methylpyridine (1a and 1 b) and 84 mg (0.4 mmol) of iron (II) chloride tetrahydrate were degassed under vacuum for 1 hour. 10 mL of dry tetrahydrofuran (THF) were added and the mixture was stirred under argon overnight at room temperature. The solid was filtered off and the filtrate was concentrated to dryness to afford 228 mg of Fe(II) complex 2 as a brown-yellow powder with a yield of 87%. It had formula C₃₅H₄₇Cl₂FeN₃ and a molar weight of 636.51 g.mol⁻¹.

Mass spectroscopy: ESI (Electron Spray Ionisation), solvent ═CH₃CN: m/z=601.28 [M-Cl]+. The calculations for C₃₅H₄₇FeClN₃ gave a value of 600.2808.

Preparation of Cr(III) Complex 3.

210 mg (0.4 mmol) of beta-diimine-methylpyridine and 162 mg (0.4 mmol) of chromium (III) chloride tetrahydrofuran were degassed under vacuum for 1 hour. 10 mL of dry tetrahydrofuran were added and the mixture was stirred under argon overnight at room temperature. The solid was filtered off and the filtrate concentrated to dryness to afford 274 mg of Cr(III) complex 3 as a pink powder with a yield of 95%. It had formula C₃₅H₄₇Cl₃CrN₃ and a molar weight of 668.13 g.mol⁻¹.

Mass spectroscopy: ESI (Electron Spray Ionisation), solvent ═CH₃CN: m/z=631.25 [M-Cl]⁺. The calculations for C₃₅H₄₇CrCl₂N₃ gave a value of 631.2552.

Preparation of Co(II) Complex 4.

51 mg (0.1 mmol) of beta-diimine-methylpyridine (1a and 1b) and 13 mg (0.1 mmol) of cobalt (II) chloride were degassed under vacuum for 1 hour. 5 mL of dry dichloromethane were added and the mixture was stirred under argon overnight at room temperature. The solid was filtered off and the filtrate was concentrated under vacuum to approximately 2 mL. 20 mL of dry pentane were added to precipitate the complex. The solvent was removed by filtration under argon and the resulting powder washed twice with 5 mL of dry pentane. The solid was dried under vacuum to afford 44 mg of Co(II) complex 4 as a green powder with a yield of 69%. It had formula C₃₅H₄₇Cl₂CoN₃ and a molar weight of 639.61 g.mol⁻¹.

Preparation of Fe(III) Complex 5.

51 mg (0.1 mmol) of beta-diimine-methylpyridine (1a and 1b) and 13 mg (0.1 mmol) of iron (III) chloride were degassed under vacuum for 1 hour. 5 mL of dry tetrahydrofuran (THF) were added and the mixture was stirred under argon overnight at room temperature. The solid was filtered off and the filtrate was concentrated to dryness to afford 45 mg of Fe complex 5 as a brown-yellow powder with a yield of 67%. It had formula C₃₅H₄₇Cl₃FeN₃ and a molar weight of 671.97 g.mol⁻¹.

Synthesis of Ligands 6

Using the procedure described for ligand 1 (step 1, 2 and 3), ligand 6 was obtained with a yield of 61%.

¹H NMR (500 MHz, CDCl₃): δ=1.26 (s, 18H, CH₃ tBu), 2.00 (s, 6H, CH₃CN), 3.63 (d, 2H, J=7.5 Hz, CH₂), 4.44 (t, 1H, J=7.5 Hz, CH), 6.25 (d, 2H, J=7.5 Hz), 7.05 (m, 6H), 7.34 (t, 2H, J=7.5 Hz), 7.62 (t, 1H, J=7.5 Hz), 8.59 (d, 1H, J=5H).

Synthesis of Ligands 7

Using the procedure described for ligand 1 (step 1, 2 and 3), ligand 7 was obtained with a yield of 41%.

¹H NMR (500 MHz, CDCl₃): δ=1.80 (s, 6H, CH₃), δ=1.84 (s, 12H, CH₃), 2.25 (s, 6H, CH₃), 3.60 (d, 2H, J=7.5 Hz, CH₂), 4.53 (t, 1H, J=7.5 Hz, CH), 6.90 (s, 4H), 7.1-7.25 (m, 1H), 7.30-7.80 (m, 3H), 8.58 (m, 1H).

Preparation of Complexes 8

Using the procedure described for complex 3, complex 8 was obtained with a yield of 68%.

Preparation of Complexes 9

Using the procedure described for complex 3, complex 9 was obtained with a yield of 63%.

Preparation of Complex 10.

150 mg (0.3 mmol) of ligand 1 and 36 mg (0.3 mmol) of chromium (II) chloride were degassed under vacuum for 1 hour. 10 mL of dry tetrahydrofuran were added and the mixture was stirred under argon overnight at room temperature. The reaction mixture was concentrated to 2 ml and 10 mL of pentane was added. The solid was filtered off and washed twice with 5 mL of pentane. The solid was dried to afford 186 mg of Cr(II) complex 10 as a green powder with a yield of 58%.

Preparation of the Complexes 11

Using the procedure described for complex 10, complex 11 was obtained with a yield of 37%.

Preparation of the Complexes 12

Using the procedure describe for complex 10, complex 12 was obtained with a yield of 46%.

High Pressure Polymerisation of Ethylene.

Ethylene polymerisation reactions were performed in a 20 mL stainless steel autoclave containing a glass insert, fitted with mechanical stirring, external thermocouple and pressure gauge and controlled by computer. In a typical reaction run, 4 mL of dry solvent (toluene or n-heptane) were introduced into the reactor, the temperature was raised to 50° C. and the ethylene pressure was raised to 15 bar and continuously fed. In a argon-filled glove box, about 5 μmol of the appropriate catalyst were weighted, activated with an amount of methylaluminoxane (MAO 30% wt in toluene) or tetraisobutyldialuminoxane (IBAO 10 wt % in toluene) activator in an amount appropriate to obtain a ratio [Al]:[M] of 2000 and diluted with toluene to a final volume of 2 mL. 200 μL of the solution of the activated catalyst were placed inside the reactor. The injection loop was rinsed with 800 μL of solvent. After 1 hour or a consumption of 12 mmol of ethylene, the reaction was quenched with isopropanol and an aliquot analysed by gas chromatography. The gas chromatographic analysis of the reaction products were performed on a Trace GC apparatus with a Petrocol capillary column (methyl silicone, 100 m long, i.d. 0.25 mm and film thickness of 0.5 μm) working at a temperature of 35° C. for 15 min and then heated to a temperature of 250° C. at a heating rate of 5° C./min. The remaining reaction mixture was quenched with MeOH/HCl and the polymer was filtered, washed with methanol and dried at a temperature of 50° C., under vacuum, for a period of time of 24 hours.

The reaction conditions for each example are displayed in Table I and the results are displayed in Table II and in Table III.

TABLE I Amt catalyst Time Example Catalyst nmol Solvent Activator min 1 2 500 toluene MAO 60 2 2 500 n-heptane MAO 60 3 3 500 toluene MAO 30 4 3 500 n-heptane MAO 60 5 3 500 n-heptane MAO 60 6 3 494 n-heptane IBAO 60 7 8 507 n-heptane MAO 60 8 9 462 n-heptane MAO 60 9 10 506 n-heptane MAO 60 10 8 507 n-heptane IBAO 60 11 9 462 n-heptane IBAO 60 12 10 506 n-heptane IBAO 60

TABLE II PE C2 cons. % C4 % C6 % αC2n Ex. mg mmol Act.^(a) Total % αC4 Total % αC6 % >C6 lin. 1 4 0.37  20 Traces — — — — 2 0 0.46  25 Traces — — — — 3 16 12.03 1350  16 99.8 27 97 57 95 4 62 2.55 140 8.5 99.5 16.5 88 75 76 5 43 2.85 160 7.5 100 16.5 89 76 86 6 551 9.96 1120^(b) — — — — — 7 68 2.44 135 Traces — — — — 8 57 2.99 181 Traces — — — — 9 60 1.62  119^(b) Traces — — — — 10 634 9.92 1252^(b) — — — — — — 11 541 9.48 1170^(b) — — — — — — 12 489 757  967^(b) — — — — — — ^(a)the activity is measured in kg of ethylene consumed per mol of metal M per hour. ^(b)the activity is measured in kg of polyethylene per mol of metal M per hour.

TABLE III DSC PE Tm ΔH GPC Example mg (° C.) J · g⁻¹ LCBI Mw Mn MWD 4 62 128.5 163.9 / / / 5 43 127.7 170.3 78270 1620 48.2 6 551 133.8 168.4 765300 31300 24.5 The molecular weight distribution for example 5 is represented in FIG. 1.

Oligomerisation of 1-hexene

In a argon-filled glove box, about 7.5 μmol of the appropriate catalyst were weighted, activated with an amount of methylaluminoxane (MAO) activator, 30% wt in toluene, suitable to give a [Al]:[M] ratio of 2000 and diluted with toluene to a final volume of 4.5 mL. 3 mL of the solution of the activated catalyst were placed in a Schlenk tube containing 5 mL of 1-hexene. The solution was stirred at a temperature of 30° C. for 1 hour. The mixture was quenched with slightly acidified methanol. The layers were separated. The toluene layer was concentrated to dryness to afford oligomers. The gas chromatographic analysis of the reaction products was done on a Trace GC apparatus with a Petrocol capillary column (methyl silicone, 100 m long, i.d. 0.25 mm and film thickness of 0.5 μm) working at a temperature of 100° C. for 4 min and then heated to a temperature of 250° C. at a heating rate of 8° C./min. The results are displayed in Table IV.

TABLE IV Amt cata. Time Yield Cata. μmol min mg Activity* % C12 % C18 % C24 2 5 60 34 4.5 0 0 0 3 5 60 277 55 57 35 8 *activity expressed in kg of oligomer per mol of metal per hour. Polymerisation of Ethylene with Supported Catalysts

Ethylene polymerisation reactions were carried out in a 130 ml stainless steel autoclave equipped with mechanical stirring and a stainless steel injection cylinder. In a typical reaction run, the reactor was first dried under nitrogen flow at 100° C. during 10 min. Then it was cooled down to the reaction temperature (50° or 85° C.) and 35 ml of isobutane were introduced into the reactor with a syringe pump, followed by the comonomer if required. The pressure was adjusted to the desired value (14.8 or 23.8 bar) with ethylene. In an argon-filled glove box, 300 mg of the supported catalyst (complex 3 deposited on MAO impregnated silica, at 2 wt % based on the total weight of the supported catalyst), the cocatalyst and 0.6 ml of n-hexane were placed into the injection cylinder. The valve was closed and the cylinder was connected to the reactor under nitrogen flow. The active catalyst mixture was then introduced into the reactor with 40 ml of isobutane. After 30 minutes or 1 hour, the reactor was cooled down to room temperature and slowly depressurised, and the polymer was recovered. The polymerisation results are displayed in Table V.

TABLE V Polymerisation results with supported Cr(III) Complex Cr T (° C.)/ Time PE Activity* Example complex P (bar) Cocatalyst min. g g/g/h 13 3 85/23.8 TiBAl 60 1.5 4.8 25.6 mg 14 3 85/23.8 TiBAl 30 1.1 7.3 25.6 mg 15 3 85/23.8 IBAO 60 1.6 5.4 38.8 mg 16 3 50/14.8 TEAl 30 0.9 5.7 16.6 mg 17^(a) 3 85/23.8 TiBAl 60 0.7 2.4 25.6 mg 18^(b) 3 85/23.8 IBAO 60 0.7 3.5 38.8 mg *Activity is expressed as g polyethylene per g catalyst per hour ^(a)0.01 Nl of H₂ was added ^(b)200 mg of catalyst was used and 1.6 ml of hexene was added

The obtained polymers were characterized by GPC in TCB at 140° C., by DSC, by RDA at 230° C. and by ¹³C NMR in TCB at 135° C. The results are displayed in table VI and FIG. 2.

TABLE VI Characterisation of the polyethylenes obtained with supported Cr(III) complex. ¹³C RDA NMR LCBI HT-GPC SCB DSC Example 230° C. Mw (Da) Mn (Da) D (mol %) Tm (° C.) 13 1.38 197081 23430 8.4 0.12 130.3 15 01.29 265464 19365 13.7 <0.1 131.7 17 / 193122 7178 26.9* / 128.8 18 2.47 243000 16200 15 / / *Bimodal

-   -   The ¹³C NMR analysis for examples 10 and 12, showed the absence         of short chain branching (less than 0.1 mol %) and the presence         of saturated and vinylic ends.

It can thus be seen that the polymers according to the present invention have a very high level of long chain branching, in fact much larger than the polymers prepared with bis-tetrahydroindenyl metallocene catalyst components known to have a high level of high chain branching and who exhibit a LCBI typically of from 0.5 to 1. 

1.-18. (canceled)
 19. A tridentate catalyst component of formula IV

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are each independently selected from hydrogen, unsubstituted or substituted hydrocarbyl, or inert functional group and two or more groups can be linked together to form further ring or rings, with the restriction that R1 and R3, R2 and R4, and R9 and R10, cannot be simultaneously oxazoline, and wherein Z is selected from groups 15 or 16 of the Periodic Table and m is the valence of Z minus one, wherein M is a metal Group 3 to 10 of the Periodic Table, wherein X′ are the same or different and are halogen or substituted or unsubstituted hydrocarbyl; and wherein n is the valence of M and characterised in that M is linked to three atoms.
 20. The tridentate catalyst component of claim 19 wherein R₁ and R₂ are unsubstituted or substituted alkyl groups, unsubstituted or substituted aryl groups, or unsubstituted or substituted cycloalkyl groups.
 21. The tridentate catalyst component of claim 19 wherein R₁ and R₂ are unsubstituted or substituted phenyl groups.
 22. The tridentate catalyst component of claim 19 wherein R3 and R4 are unsubstituted or substituted alkyl groups, unsubstituted or substituted aryl groups, or unsubstituted or substituted cycloalkyl groups.
 23. The tridentate catalyst component of claim 19 wherein R₃ and R₄ are unsubstituted or substituted alkyl groups.
 24. The tridentate catalyst component of claim 23 wherein R₃ and R₄ are linked together to form a cyclohexyl ring.
 25. The tridentate catalyst component of claim 19 wherein R₅ is hydrogen or methyl.
 26. The tridentate catalyst component of claim 19 wherein Z is N, P, O or S.
 27. The tridentate catalyst component of claim 19 claims wherein R₆, R₇, R₈, R₉ and R₁₀ are unsubstituted or substituted alkyl groups, unsubstituted or substituted aryl groups, or unsubstituted or substituted cycloalkyl groups.
 28. The tridentate catalyst component of claim 9 wherein M is Ti, Zr, Hf, V, Cr, Mn, Fe, Co, Ni, or Pd.
 29. The tridentate catalyst component of claim 10 wherein M is Cr.
 30. A method for preparing the tridentate catalyst component of any one of claims 1 to 11 by complexing a ligand of formula I

with a metallic salt MX′_(n) in a solvent, wherein all Ri's and M are as defined in claim 19, wherein X is halogen or substituted or unsubstituted hydrocarbyl and n is the valence of M.
 31. An active catalyst system comprising the tridentate catalyst component of claim 19 and an activating agent having an ionising action and optionally a cocatalyst.
 32. An active catalyst system comprising the tridentate catalyst component of claim 19, an activating support and optionally a cocatalyst.
 33. A method for oligomerising or homo- or co-polymerising ethylene and alpha-olefins that comprises: a) injecting the active catalyst system of claim 31 or claim 32 into the reactor; b) injecting ethylene monomer and optional comonomer either before or after or simultaneously with step a); c) maintaining polymerisation conditions; d) retrieving oligomers or a polymer.
 34. The method of claim 33 wherein the monomer and optional comonomer are selected from ethylene, propylene or 1-hexene.
 35. The method of claim 34 wherein the optional comonomer is a polar functionalised alpha-olefin. 